EP0853593A4 - Synthetisches, poröses, kristallines mcm 61, dessen synthese und verwendung - Google Patents

Synthetisches, poröses, kristallines mcm 61, dessen synthese und verwendung

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Publication number
EP0853593A4
EP0853593A4 EP96935867A EP96935867A EP0853593A4 EP 0853593 A4 EP0853593 A4 EP 0853593A4 EP 96935867 A EP96935867 A EP 96935867A EP 96935867 A EP96935867 A EP 96935867A EP 0853593 A4 EP0853593 A4 EP 0853593A4
Authority
EP
European Patent Office
Prior art keywords
crystalline material
mixture
composition
crown
sorbent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96935867A
Other languages
English (en)
French (fr)
Other versions
EP0853593A1 (de
EP0853593B1 (de
Inventor
Ernest W Valyocsik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil AS
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Filing date
Publication date
Application filed by Mobil Oil AS filed Critical Mobil Oil AS
Publication of EP0853593A1 publication Critical patent/EP0853593A1/de
Publication of EP0853593A4 publication Critical patent/EP0853593A4/de
Application granted granted Critical
Publication of EP0853593B1 publication Critical patent/EP0853593B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles

Definitions

  • This invention relates to a synthetic porous crystalline material, MCM-61, to a method for its preparation and to its use as a sorbent or in catalytic conversion of organic or inorganic compounds.
  • Zeolitic materials both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion.
  • Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These cavities and pores are uniform in size within a specific zeolitic material.
  • molecular sieves are utilized in a variety of ways to take advantage of these properties.
  • Such molecular sieves include a wide variety of positive ion-containing crystalline silicates. These silicates can be described as a rigid three-dimensional framework of SiO. and Periodic Table Group IIIA element oxide, e.g., AIO., in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total Group IIIA element, e.g., aluminum, and silicon atoms to oxygen atoms is 1:2.
  • the electrovalence of the tetrahedra containing the Group IIIA element, e.g., aluminum, is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation.
  • a cation for example an alkali metal or an alkaline earth metal cation.
  • This can be expressed wherein the ratio of the Group IIIA element, e.g., aluminum, to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity.
  • One type of cation may be exchanged either entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the properties of a given silicate by suitable selection of the cation.
  • the spaces between the tetrahedra are occupied by molecules of water prior to dehydration.
  • zeolite A U.S. Patent 2,882,243
  • zeolite X U.S. Patent 2,882,244
  • zeolite Y U.S. Patent 3,130,007
  • zeolite ZK-5 U.S. Patent 3,247,195
  • zeolite ZK-4 U.S. Patent 3,314,752
  • zeolite ZSM-5 U.S. Patent 3,702,886
  • zeolite ZSM-11 U.S. Patent 3,709,979
  • zeolite ZSM-12 U.S.
  • Patent 3,832,449) zeolite ZSM-20 (U.S. Patent 3,972,983); ZSM-35 (U.S. Patent 4,016,245); zeolite ZSM-23 (U.S. Patent 4,076,842); zeolite MCM-22 (U.S. Patent 4,954,325); and zeolite MCM-35 (U.S. Patent 4,981,663) .
  • the SiO-/Al_0_ ratio of a given zeolite is often variable.
  • zeolite X can be synthesized with SiO /Al-,0 ratios of from 2 to 3; zeolite Y, from 3 to about 6.
  • the upper limit of the SiO_/Al_0_ ratio is unbounded.
  • ZSM-5 is one such example wherein the Si0,/Al 0 ratio is at least 5 and up to the limits of present analytical measurement techniques.
  • U.S. Patent 3,941,871 discloses a porous crystalline silicate made from a reaction mixture containing no deliberately added alumina in the recipe and exhibiting the X-ray diffraction pattern characteristic of ZSM-5.
  • U.S. Patents 4,061,724, 4,073,865 and 4,104,294 describe crystalline silicate of varying alumina and metal content.
  • the invention resides in a porous crystalline material, named MCM-61, characterized by an X- ray diffraction pattern including values substantially as set forth in Table I below.
  • the invention resides a process for synthesizing a porous crystalline material exhibiting a characteristic X-ray diffraction pattern including d- spacing maxima values shown in Table I which comprises (i) preparing a mixture capable of forming said material, said mixture comprising sources of potassium (M) , an oxide of trivalent element (X) , an oxide of tetravalent element (Y) , water, and directing agent (R) comprising a crown ether selected from 15-Crown-5, 18-Crown-6 and mixtures thereof, and having a composition, in terms of mole ratios, within the following ranges:
  • the crystalline MCM-61 material of the invention appears to be a single crystalline phase. It can be prepared in essentially pure form with little or no detectable impurity crystal phases and has an X-ray diffraction pattern in the calcined form which is distinguished from the patterns of other known as- synthesized or thermally treated crystalline materials by the lines listed in Table I below: TABLE I
  • X-ray diffraction data were collected with a Scintag diffraction system, equipped with a germanium solid state detector, using copper K-alpha radiation.
  • the diffraction data were recorded by step-scanning at 0.05 degrees of two- theta, where theta is the Bragg angle, and a counting time of 1 second for each step.
  • the interplanar spacings, d's were calculated in Angstrom units (A) , and the relative intensities of the lines, I/I s one-hundredth of the intensity of the strongest line, above background, were derived with the use of a profile fitting routine (or second derivative algorithm) .
  • the intensities are uncorrected for Lorentz and polarization effects.
  • the crystalline material of this invention has a composition involving the molar relationship:
  • X 2 0 3 (n)Y0 2
  • X is a trivalent element, such as aluminum, boron, iron, indium, and/or gallium, preferably aluminum
  • Y is a tetravalent element such as silicon, tin, and/or germanium, preferably silicon
  • n is from 15 to 200, usually from 30 to about 90.
  • the material has a formula, on an anhydrous basis and in terms of moles of oxides per n moles of YO_, as follows:
  • M comprises potassium
  • R is an organic moiety.
  • M and R components are associated with the material as a result of their presence during crystallization, and are easily removed by post-crystallization methods hereinafter more particularly described.
  • the crystalline material of the invention is thermally stable and in the calcined form exhibits significant hydrocarbon sorption capacity.
  • the original potassium cations of the as-synthesized material can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations.
  • Preferred replacing cations include metal ions, hydrogen ions, hydrogen precursor, e.g., ammonium, ions and mixtures thereof.
  • Particularly preferred cations are those which tailor the catalytic activity for certain hydrocarbon conversion reactions. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Table of the Elements.
  • the crystalline material of the invention When used as a catalyst, the crystalline material of the invention may be subjected to treatment to remove part or all of any organic constituent.
  • thermal treatment which is generally performed by heating at a temperature of at least 370°C for at least 1 minute and generally not longer than 20 hours. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is desired for reasons of convenience.
  • the thermal treatment can be performed at a temperature up to 925°C.
  • the thermally treated product, especially in its metal, hydrogen and ammonium forms, is particularly useful in the catalysis of certain organic, e.g., hydrocarbon, conversion reactions.
  • the crystalline material can also be used as a catalyst in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation- dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation- dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation- dehydrogenation function is to be performed.
  • Such component can be in the composition by way of cocrystallization, exchanged into the composition to the extent
  • Such component can be impregnated in or on to it such as, for example, by, in the case of platinum, treating the silicate with a solution containing a platinum metal-containing ion.
  • suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
  • the crystalline material of this invention when employed either as an adsorbent or as a catalyst in an organic compound conversion process should be dehydrated, at least partially. This can be done by heating to a temperature in the range of 200°C to 370°C in an atmosphere such as air, nitrogen, etc. , and at atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes and 48 hours. Dehydration can also be performed at room temperature merely by placing the MCM-61 in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
  • the present crystalline material can be prepared from a reaction mixture containing sources of potassium (M) cations, an oxide of trivalent element X, e.g., aluminum and/or boron, an oxide of tetravalent element Y, e.g., silicon, directing agent (R) , and water, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:
  • the preferred source of YO comprises predominately solid Y0 2 , for example at - ⁇ - least about 30 wt.% solid YO-,.
  • YO is silica
  • the use of a silica source containing at least about 30 wt.% solid silica e.g., Ultrasil (a precipitated, spray dried silica containing about 90 wt.% silica) or HiSil (a precipitated hydrated SiO-, containing about 87 wt.% silica, about 6 wt.% free H-,0 and about 4.5 wt.% bound H_0 of hydration and having a particle size of about 0.02 micron) is preferred for MCM-58 formation from the above mixture.
  • Ultrasil a precipitated, spray dried silica containing about 90 wt.% silica
  • HiSil a precipitated hydrated SiO-, containing about 87 wt.% silica, about 6 wt.%
  • the 0 2 e.g., silica
  • the 0 2 e.g., silica
  • the 0 2 e.g., silica
  • the 0 2 e.g., silica
  • the 0 2 contains at least about 30 wt.% solid YO , e.g., silica, and more preferably at least about 40 wt.% solid YO , e.g., silica.
  • the organic directing agent R for use herein is a crown ether selected from the group consisting of 15-Crown- 5, 18-Crown-6 and combinations thereof. These compounds may be represented as follows:
  • Crystallization of the present crystalline material can be carried out at either static or stirred conditions in a suitable reactor vessel, such as for example, polypropylene jars or teflon lined or stainless steel autoclaves. Crystallization is generally perfromed at a temperature of 80°C to 250°C for a time sufficient for crystallization to occur, normally from 12 hours to 100 days. Thereafter, the crystals are separated from the liquid and recovered.
  • a suitable reactor vessel such as for example, polypropylene jars or teflon lined or stainless steel autoclaves. Crystallization is generally perfromed at a temperature of 80°C to 250°C for a time sufficient for crystallization to occur, normally from 12 hours to 100 days. Thereafter, the crystals are separated from the liquid and recovered.
  • reaction mixture components can be supplied by more than one source.
  • the reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time of the new crystalline material will vary with the nature of the reaction mixture employed and the crystallization conditions. Synthesis of the new crystals may be facilitated by the presence of at least 0.01 percent, preferably 0.10 percent and still more preferably 1 percent, seed crystals (based on total weight) of crystalline product.
  • the crystalline material of this invention can be used to catalyze a wide variety of chemical conversion processes including many of present commercial/industrial importance. Examples of chemical conversion processes which are effectively catalyzed by the crystalline material of this invention, by itself or in combination with one or more other catalytically active substances including other crystalline catalysts, include those requiring a catalyst with acid activity. Specific examples include:
  • reaction conditions including a temperature of 200°C to 760°C, a pressure of 100 to 6000 kPa (1 to 60 atmospheres) , a weight hourly space velocity (WHSV) of 0.1 hr ⁇ to 20 hr '1 , and a hydrogen/hydrocarbon mole ratio of from 0 (no added hydrogen) to about 50, to provide disproportionation product, including p-xylene;
  • WHSV weight hourly space velocity
  • reaction conditions including a temperature of 100°C to 500°C, a pressure of 100 to 20000 kPa (1 to 200 atmospheres), and a WHSV of 1 hr "1 to 10,000 hr "1 ;
  • reaction of paraffins with aromatics to form alkylaromatics and light gases with reaction conditions including a temperature of 260°c to 375°C, a pressure of 100 to 7000 kPa (0 to 1000 psig), a WHSV of 0.5 hr "1 to 10 hr '1 , and a hydrogen/hydrocarbon mole ratio of 0 (no added hydrogen) to 10;
  • paraffin isomerization to provide branched paraffins with reaction conditions including a temperature of 200°C to 315°C, a pressure of 800 to 7000 kPa (100 to 1000 psigO, a WHSV of 0.5 hr "1 to 10 hr "1 , and a hydrogen/hydrocarbon mole ratio of 0.5 to 10; and
  • alkyiation of aromatics with olefins with reaction conditions including a temperature of 200°C to 500°C, a pressure of 100 to 3550 kPa (0 to 500 psig) , a total WHSV of 0.5 hr "1 to 50 hr '1 , a hydrogen/hydrocarbon mole ratio of from 0 (no added hydrogen) to 10, and an aromatic/olefin mole ratio of from 1 to 50.
  • the crystalline material of this invention can also be used as a sorbent or as a sorbent for separation of substances from mixtures thereof.
  • At least one component may be separated from a mixture of components in the vapor or liquid phase having differential sorption characteristics with respect to the MCM-61 sorbent by contacting the mixture containing the components with the MCM-61 sorbent to selectively sorb from the mixture and onto the sorbent at least one component of the mixture, so as to effect a selective separation of the at least one sorbed component from the remaining at least one unsorbed component of the mixture.
  • the mixture may comprise water and at least one hydrocarbon component, at least one hydrocarbon component of the mixture being selectively sorbed on the MCM-61 sorbent in preference to the water in the mixture.
  • the sorption process may involve a mixture comprising at least two hydrocarbon components, at least one of which is selectively sorbed on the MCM-61 sorbent in preference to at least one other hydrocarbon component of the mixture.
  • the sorption separation of this invention may involve a mixture comprising an alcohol and at least one hydrocarbon component, at least one hydrocarbon component of the mixture being selectively sorbed on the MCM-61 sorbent in preference to the alcohol in the mixture.
  • Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina.
  • the latter may be either naturally occurring or in the form -ll ⁇ Of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction.
  • These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions.
  • Said materials i.e., clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
  • Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with the present crystal also include inorganic oxides, such as silica, zirconia, titania, magnesia, berylIia, alumina, and mixtures thereof.
  • the new crystal can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica- alumina-zirconia silica-alumina-magnesia and silica- magnesia-zirconia.
  • a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica- alumina-zirconia silica-alumina-magnesia and silica- magnesia-zirconia.
  • the relative proportions of finely divided crystalline material and inorganic oxide matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight, and more usually from 2 to 80 percent by weight, of the composite.
  • a weighed sample of the calcined adsorbent was contacted with the desired pure adsorbate vapor in an adsorption chamber, evacuated to less than 1 mm and contacted with 5.3 kPa (40 Torr) of cyclohexane vapor or
  • the Alpha Test is described in U.S. Patent 3,354,078; in the Journal Of Catalysis, 4, 527 (1965); 6, 278 (1966); and 61, 395 (1980).
  • the experimental conditions of the test used herein include a constant temperature of 538°C and a variable flow rate as described in detail in the Journal of Catalysis. 61, 395.
  • the air calcined samples were ammonium exchanged with 1 M NH 4 N0 3 at 80°C for 6 hours. After ammonium exchange, the zeolites were filtered, washed with deionized water, and dried in an air stream on the filter funnel under an infrared heat lamp.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP96935867A 1995-10-02 1996-09-20 Synthetisches, poröses, kristallines mcm 61, dessen synthese und verwendung Expired - Lifetime EP0853593B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US467195P 1995-10-02 1995-10-02
US4671P 1995-10-02
PCT/US1996/015039 WO1997012838A1 (en) 1995-10-02 1996-09-20 Synthetic porous crystalline mcm-61, its synthesis and use

Publications (3)

Publication Number Publication Date
EP0853593A1 EP0853593A1 (de) 1998-07-22
EP0853593A4 true EP0853593A4 (de) 1999-01-27
EP0853593B1 EP0853593B1 (de) 2001-08-22

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96935867A Expired - Lifetime EP0853593B1 (de) 1995-10-02 1996-09-20 Synthetisches, poröses, kristallines mcm 61, dessen synthese und verwendung

Country Status (9)

Country Link
US (1) US5670131A (de)
EP (1) EP0853593B1 (de)
JP (1) JPH11512696A (de)
KR (1) KR19990036416A (de)
AU (1) AU697160B2 (de)
CA (1) CA2228177A1 (de)
DE (1) DE69614701T2 (de)
DK (1) DK0853593T3 (de)
WO (1) WO1997012838A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6888035B2 (en) 2000-09-25 2005-05-03 Exxonmobil Chemical Patents Inc. Hydrogenation of cleavage effluents in phenol production
EP1343725B1 (de) * 2000-12-08 2008-03-26 ExxonMobil Chemical Patents Inc. Kristalline molekularsiebe
CN101332433B (zh) * 2007-06-27 2011-07-20 中国石油化工股份有限公司 一种催化裂化催化剂及其制备和应用方法
US8546287B2 (en) * 2010-05-31 2013-10-01 Fina Technology, Inc. Rhenium promoted catalyst
US9416017B2 (en) * 2014-07-03 2016-08-16 Chevron U.S.A. Inc. Method for making molecular sieve SSZ-98
KR101996273B1 (ko) * 2017-12-19 2019-07-04 한밭대학교 산학협력단 합성제올라이트를 활용한 라돈가스 저감 건축용 보드 및 이의 제조방법
CN111646485A (zh) * 2020-04-28 2020-09-11 北京泷涛环境科技有限公司 多级孔分子筛及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377502A (en) * 1979-12-26 1983-03-22 Standard Oil Company (Indiana) Synthesis of crystalline aluminosilicate molecular sieves
WO1991001940A1 (fr) * 1989-08-02 1991-02-21 Societe Nationale Elf Aquitaine Synthese de zeolites gallosilicate a structure faujasite
EP0554922A2 (de) * 1988-10-10 1993-08-11 Elf Aquitaine Aluminosilikatzeolith bestehend aus einem hexagonalen Polytyp des Faujasits
EP0595703A1 (de) * 1992-10-26 1994-05-04 Societe Nationale Elf Aquitaine Verfahren zur Synthese von Zeolithen, die zur strukturellen Familie des Faujasits gehören
EP0796821A1 (de) * 1996-03-21 1997-09-24 ENIRICERCHE S.p.A. Zeolith ERS-10 und Verfahren zu seiner Herstellung

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Publication number Priority date Publication date Assignee Title
US3950496A (en) * 1973-05-29 1976-04-13 Mobil Oil Corporation Synthetic zeolite ZSM-18
JPS5926924A (ja) * 1982-07-30 1984-02-13 Res Assoc Petroleum Alternat Dev<Rapad> 結晶性シリケートの製造方法
US4556549A (en) * 1983-11-29 1985-12-03 Mobil Oil Corporation Process for making zeolite ZSM-45 with an organocobalt complex
US5252527A (en) * 1988-03-23 1993-10-12 Chevron Research And Technology Company Zeolite SSZ-32
US5393511A (en) * 1988-10-10 1995-02-28 Societe Nationale Elf Aquitaine Synthesis of zeolites of faujasite structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377502A (en) * 1979-12-26 1983-03-22 Standard Oil Company (Indiana) Synthesis of crystalline aluminosilicate molecular sieves
EP0554922A2 (de) * 1988-10-10 1993-08-11 Elf Aquitaine Aluminosilikatzeolith bestehend aus einem hexagonalen Polytyp des Faujasits
WO1991001940A1 (fr) * 1989-08-02 1991-02-21 Societe Nationale Elf Aquitaine Synthese de zeolites gallosilicate a structure faujasite
EP0595703A1 (de) * 1992-10-26 1994-05-04 Societe Nationale Elf Aquitaine Verfahren zur Synthese von Zeolithen, die zur strukturellen Familie des Faujasits gehören
EP0796821A1 (de) * 1996-03-21 1997-09-24 ENIRICERCHE S.p.A. Zeolith ERS-10 und Verfahren zu seiner Herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9712838A1 *

Also Published As

Publication number Publication date
AU7365196A (en) 1997-04-28
AU697160B2 (en) 1998-10-01
WO1997012838A1 (en) 1997-04-10
DE69614701T2 (de) 2002-03-07
DK0853593T3 (da) 2001-10-08
CA2228177A1 (en) 1997-04-10
EP0853593A1 (de) 1998-07-22
EP0853593B1 (de) 2001-08-22
JPH11512696A (ja) 1999-11-02
US5670131A (en) 1997-09-23
DE69614701D1 (de) 2001-09-27
KR19990036416A (ko) 1999-05-25

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